US5015708A - Precipitation polymerization of terpolymers of a vinyl lactam, a polymerizable carboxylic acid and a hydrophobic monomer in an aliphatic hydrocarbon solvent - Google Patents

Precipitation polymerization of terpolymers of a vinyl lactam, a polymerizable carboxylic acid and a hydrophobic monomer in an aliphatic hydrocarbon solvent Download PDF

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Publication number
US5015708A
US5015708A US07/373,012 US37301289A US5015708A US 5015708 A US5015708 A US 5015708A US 37301289 A US37301289 A US 37301289A US 5015708 A US5015708 A US 5015708A
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United States
Prior art keywords
precipitation polymerization
polymerization process
process according
carboxylic acid
vinyl
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US07/373,012
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Jenn S. Shih
Terry E. Smith
Robert B. Login
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ISP CAPITAL Inc
ISP Investments LLC
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GAF Chemicals Corp
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Assigned to GAF CHEMICALS CORPORATION reassignment GAF CHEMICALS CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: LOGIN, ROBERT B., SHIH, JENN S., SMITH, TERRY E.
Priority to US07/373,012 priority Critical patent/US5015708A/en
Priority to DE69017025T priority patent/DE69017025T2/de
Priority to EP90910019A priority patent/EP0479856B1/de
Priority to DK90910019.0T priority patent/DK0479856T3/da
Priority to PCT/US1990/003259 priority patent/WO1991000302A1/en
Priority to JP2509227A priority patent/JP2991491B2/ja
Priority to AT90910019T priority patent/ATE118512T1/de
Priority to KR1019910701863A priority patent/KR0149171B1/ko
Priority to ES90910019T priority patent/ES2070325T3/es
Priority to AU58498/90A priority patent/AU630714B2/en
Priority to CA002019556A priority patent/CA2019556C/en
Assigned to CHASE MANHATTAN BANK (NATIONAL ASSOCIATION), THE reassignment CHASE MANHATTAN BANK (NATIONAL ASSOCIATION), THE SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: GAF CHEMICALS CORPORATION, A CORP. OF DE
Publication of US5015708A publication Critical patent/US5015708A/en
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Assigned to ISP INVESTMENTS INC. reassignment ISP INVESTMENTS INC. CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). EFFECTIVE ON 06/06/1991 Assignors: ISP 3 CORP.
Assigned to ISP 3 CORP reassignment ISP 3 CORP ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: GAF CHEMICALS CORPORATION
Assigned to GAF BUILDING MATERIALS CORPORATION, GAF CHEMICALS CORPORATION, SUTTON LABORATORIES, INC. reassignment GAF BUILDING MATERIALS CORPORATION RELEASED BY SECURED PARTY (SEE DOCUMENT FOR DETAILS). Assignors: CHASE MANHATTAN BANK, THE (NATIONAL ASSOCIATION)
Assigned to ISP CAPITAL, INC. reassignment ISP CAPITAL, INC. CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: ISP INVESTMENTS, INC.
Assigned to CHASE MANHATTAN BANK, THE reassignment CHASE MANHATTAN BANK, THE SECURITY AGREEMENT Assignors: ISP CAPITAL, INC.
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Assigned to VERONA, INC., ISP CAPITAL, INC., ISP CHEMICAL PRODUCTS, INC. reassignment VERONA, INC. PATENT RELEASE Assignors: JPMORGAN CHASE BANK, N.A. (F/K/A THE CHASE MANHATTAN BANK)
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F26/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F26/06—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • C08F26/10—N-Vinyl-pyrrolidone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • C08F226/10—N-Vinyl-pyrrolidone
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3776—Heterocyclic compounds, e.g. lactam

Definitions

  • This invention relates to terpolymers of a vinyl lactam, a polymerizable carboxylic acid and a hydrophobic monomer, and, more particularly, to precipitation polymerization of such terpolymers within a defined compositional range, prepared in high yield, as a white powder, which can be filtered and dried easily.
  • Straub, F. et al. in U.S. Pat. No. 4,595,737 prepared water soluble terpolymers of a vinyl lactam, acrylic acid and 50-80% of a C 1 -C 4 alkyl vinyl ether by solution polymerization in alcohol or a cyclic ether.
  • the product was a viscous mass which was very difficult to filter; it was isolated by casting a film of the terpolymer and evaporating the solvent.
  • Blank, I. and Fertig, J., in U.S. Pat. No. 4,248,855 described a series of terpolymers of vinyl pyrrolidone, acrylic acid and methyl acrylate, prepared by solution and emulsion polymerization.
  • Precipitation polymerization is a known method for preparing polymers as a powder which can be filtered and dried easily; it is available when the monomers are adequately soluble in the reaction solvent and the polymer is insoluble in the solvent.
  • a commercially successful precipitation polymerization process must provide a precipitate of the polymer as a powder, in a non-toxic solvent, in high yield, which is easy to filter, and within a desired polymer compositional range.
  • the polymerization is carried out in a reaction mixture of predetermined composition of a vinyl lactam, e.g. vinyl pyrrolidone or vinyl caprolactam, a polymerizable carboxylic acid, e.g. acrylic acid or methacrylic acid, and a hydrophobic monomer, e.g. lauryl methacrylate, in the presence of a polymerization initiator, e.g.
  • a vinyl lactam e.g. vinyl pyrrolidone or vinyl caprolactam
  • a polymerizable carboxylic acid e.g. acrylic acid or methacrylic acid
  • a hydrophobic monomer e.g. lauryl methacrylate
  • a free radical initiator in an aliphatic hydrocarbon solvent, preferably, a C 3 -C 10 saturated, branched or unbranched, cyclic or acyclic, and, particularly, heptane or cyclohexane.
  • the precipitation polymerization process herein provides terpolymers having a compositional range of 20-90% by wt. vinyl lactam, 1-55% by wt. polymerizable carboxylic acid, and 1-25% by wt. hydrophobic monomer, as a white powder, which powder precipitates readily from the aliphatic hydrocarbon solvent in high yield and is easily isolated.
  • the terpolymer comprises about 40-70% vinyl lactam, 15-40% polymerizable carboxylic acid, and 5-20% hydrophobic monomer.
  • terpolymers of a vinyl lactam, a polymerizable carboxylic acid and a hydrophobic monomer are made by a precipitation polymerization process in an aliphatic hydrocarbon solvent in the presence of a polymerization initiator.
  • Suitable vinyl lactams for use herein include vinyl pyrrolidone, vinyl caprolactam and alkylated vinyl derivatives thereof.
  • Suitable polymerizable carboxylic acids include acrylic acid, methacrylic acid, itaconic acid and crotonic acid.
  • Suitable hydrophobic monomers include ⁇ -olefins, alkyl vinyl ethers, alkyl esters of polymerizable carboxylic acids, polymerizable N-alkyl and N,N-dialkyl acryl amides, vinyl esters of carboxylic acids, N-alkyl diallyl amines, and salts thereof, and, preferably where the alkyl group has at least 6 carbon atoms; polymerizable silicon alkyl compounds; and polymerizable fluorinated alkyl monomers; and mixtures of the above.
  • hydrophobic monomers include: ⁇ -olefins, such as hexadecene, octadecene and p-propyl styrene; alkyl vinyl ethers, such as octadecyl vinyl ether and hexadecyl vinyl ether; alkyl esters of polymerizable carboxylic acids, such as 2-ethylhexyl acrylate and methacrylate, octyl acrylate and methacrylate, lauryl acrylate and methacrylate, and stearyl acrylate and methacrylate; polymerizable N-alkyl and N,N-dialkyl acrylamides, such as N-dodecyl methacrylamide, N-octadecyl methacrylamide and N,N-dihexyl methacrylamide; vinyl esters of carboxylic acids, such as vinyl octanoate, vinyl hexade
  • the terpolymers made by the precipitation polymerization process of the invention have a compositional range of 20-90% by wt. vinyl lactam, 1-55% by wt. polymerizable carboxylic acid, and 1-25% by wt. of hydrophobic monomer.
  • the terpolymers comprise about 40-70% by wt. vinyl lactam, 15-40% by wt. polymerizable carboxylic acid, and 5-20% by wt. hydrophobic monomer.
  • the precipitation polymerization process of the invention can provide the terpolymer in a yield of 80% or more, preferably 90-98%, as a powder, which powder can be filtered and recovered easily.
  • the reaction solvent in the precipitation polymerization process of the invention suitably is a C 3 -C 10 saturated hydrocarbon which is branched or unbranched, cyclic or acyclic.
  • the solvent is a C 5 -C 8 aliphatic hydrocarbon or mixtures thereof.
  • a preferred aliphatic hydrocarbon solvent over other known precipitation polymerization solvents is selected from heptane and cyclohexane.
  • Heptane the most preferred solvent, provides high yields of a precipitate of the desired terpolymer composition as a fine white powder which is easy to filter and dry.
  • the amount of solvent used in the process of the invention should be sufficient to dissolve an appreciable amount of the reactants and to maintain the terpolymer precipitate in a stirrable state at the end of the polymerization. Generally, up to about 40% solids, preferably 15-20% solids, is maintained in the reaction mixture.
  • the precipitation polymerization process of the invention is carried out in the presence of a polymerization initiator, preferably a free radical initiator, and most suitably, a peroxy ester, e.g. t-butylperoxy pivalate, although other free radical initiators such as acylperoxides, alkyl peroxides and azonitriles, known in the art, may be used as well.
  • a polymerization initiator preferably a free radical initiator, and most suitably, a peroxy ester, e.g. t-butylperoxy pivalate, although other free radical initiators such as acylperoxides, alkyl peroxides and azonitriles, known in the art, may be used as well.
  • the amount of such initiator may vary widely; generally about 0.2-5.0% is used, based on the weight of total monomers charged.
  • the reaction temperature may vary widely; generally the reactants are maintained at about 50°-150° C., preferably 60°-70° C., during the polymerization. Pressure usually is kept at atmospheric pressure, although higher and lower pressures may be used as well.
  • the reaction mixture should be stirred vigorously under an inert atmosphere, e.g. nitrogen, during the polymerization.
  • a stirring rate of about 400-600 rpm in a 1-liter lab reactor is quite adequate to effect the desired polymerization and to keep the precipitate in a stirrable state during the polymerization.
  • the precipitation polymerization process of the invention may be carried out by first precharging a suitable reactor with a predetermined amount of a vinyl lactam in the aliphatic hydrocarbon solvent, and heating the mixture to the desired reaction temperature while stirring vigorously under an inert gas atmosphere. The initiator is then charged into the reactor. Then selected amounts of the polymerizable carboxylic acid and the hydrophobic monomer are admitted into the reactor over a period of time, generally about an hour or more. The reaction mixture then is held for an additional period of time for polymerization to occur. Finally, the mixture is cooled to room temperature. Filtering, washing with solvent, and drying provide the terpolymer in yields approaching quantitative, and, substantially, in a composition predetermined by the weight ratio of monomers introduced into the reactor.
  • the aliphatic hydrocarbon solvent can be precharged into the reactor, purged with nitrogen, heated to the reaction temperature, the initiator added, and then separate streams of the vinyl lactam monomer, the acrylic acid monomer and the hydrophobic monomer can be introduced over a period of time into the precharged reactor.
  • Other process variations will be apparent to those skilled in the art.
  • a 1-liter, 5-necked reaction kettle was equipped with a condenser, a thermometer, a nitrogen purge tube, two dropping funnels, and a mechanical stirrer.
  • the reactor was precharged with vinyl pyrrolidone (VP) in 500 g. of heptane.
  • VP vinyl pyrrolidone
  • the mixture then was heated to 65° C. in nitrogen gas and held for 30 minutes.
  • t-Butyl peroxypivalate 260 microliter
  • acrylic acid (AA) and lauryl methacrylate (LM) were added over 1 hour. Additional t-butyl peroxypivalate (140 microliter) was charged after 2 hours.
  • the reaction mixture then was held at 65° C. for another 2 hours.
  • the mixture was filtered, washed with heptane twice and dried in an oven overnight at 100° C.
  • the white powder obtained then was dried in a vacuum oven at 100° C. overnight.
  • Table 1 The results are shown in Table 1 below.
  • Examples 1-11 and the comparative examples A and B above demonstrate that successful precipitation polymerization of terpolymers of vinyl pyrrolidone, acrylic acid and lauryl methacrylate or stearyl methacrylate is dependent upon the compositional range of the monomer reactants. In particular, greater than about 30% of the hydrophobic monomer precludes an effective precipitation polymerization process, the yield of terpolymer dropping to unacceptable levels.
  • a 1-liter reaction kettle was equipped with condenser, a thermometer, a nitrogen purge tube, two dropping funnels, and a mechanical stirrer.
  • the reactor was precharged with vinyl pyrrolidone and 500 g. of heptane. The mixture then was heated to 65° C. in nitrogen gas and held there for 30 min.
  • t-Butyl peroxypivalate (260 microliter) was charged and acrylic acid and trimethyloxysilylpropyl methacrylate (TMSPM) or polydimethylsiloxane, monomethacryloxypropyl terminated (DMMBMA) were added over an hour.
  • TMSPM trimethyloxysilylpropyl methacrylate
  • DMMBMA monomethacryloxypropyl terminated
  • a 1-liter reaction kettle was equipped with a condenser, a thermometer, a nitrogen purge tube, two dropping funnels and a mechanical stirrer. 500 g. of heptane was charged. The solution was heated to 65° C. and held at that temperature for 30 minutes with nitrogen purge. 260 microliter of t-butyl peroxypivalate was added and vinyl pyrrolidone (75 g.), dodecyl vinyl ether (20 g.) and acrylic acid (25 g.) were charged simultaneously over 1 hour. The mixture was heated to 85° C. over a half-hour and held at 85° C. for another half-hour.
  • Example 16 The procedure of Example 16 was followed except that VP, AA and perfluorooctyl methacrylate, 20 g., in 16 g. of acetone, was fed separately into the reactor precharged with heptane. Yield: 87%.
  • Example 16 The procedure of Example 16 was followed using 20 g. of vinyl acetate in place of dodecyl vinyl ether. Yield: 90%.
  • a 1-liter reaction kettle was equipped with a condenser, a thermometer, a nitrogen purge tube, two dropping funnels and a mechanical stirrer. 500 g. of heptane and 20 g. of 1-hexadecene were charged. The solution was heated to 65° C. and held at that temperature for 30 minutes while purging with nitrogen. 260 microliter of t-butyl peroxypivalate was added and vinyl pyrrolidone (75 g.) and acrylic acid (25 g.) were charged simultaneously over 1 hour. The mixture was heated to 85° C. over a half-hour and held at 85° C. for another half-hour.
  • the terpolymer products of the invention find particular utility in such applications as thickeners, adhesives, in paper manufacture and coatings thereon, in ion-exchange resins and membranes, in controlled release polymers, in textile sizings, as dispersants, in oil recovery chemicals, in surface cleaning, as anti-scaling agents in boilers, and in personal care products.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
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US07/373,012 1989-06-26 1989-06-26 Precipitation polymerization of terpolymers of a vinyl lactam, a polymerizable carboxylic acid and a hydrophobic monomer in an aliphatic hydrocarbon solvent Expired - Lifetime US5015708A (en)

Priority Applications (11)

Application Number Priority Date Filing Date Title
US07/373,012 US5015708A (en) 1989-06-26 1989-06-26 Precipitation polymerization of terpolymers of a vinyl lactam, a polymerizable carboxylic acid and a hydrophobic monomer in an aliphatic hydrocarbon solvent
DE69017025T DE69017025T2 (de) 1989-06-26 1990-06-14 Niederschlagpolymerisierung von vinyllaktamterpolymeren.
EP90910019A EP0479856B1 (de) 1989-06-26 1990-06-14 Niederschlagpolymerisierung von vinyllaktamterpolymeren
DK90910019.0T DK0479856T3 (da) 1989-06-26 1990-06-14 Udfældelsespolymerisering af vinyllactamterpolymerer
PCT/US1990/003259 WO1991000302A1 (en) 1989-06-26 1990-06-14 Precipitation polymerization of vinyl lactam terpolymers
JP2509227A JP2991491B2 (ja) 1989-06-26 1990-06-14 ビニルラクタム三元共重合体の沈殿重合
AT90910019T ATE118512T1 (de) 1989-06-26 1990-06-14 Niederschlagpolymerisierung von vinyllaktamterpolymeren.
KR1019910701863A KR0149171B1 (ko) 1989-06-26 1990-06-14 비닐락탐 삼원공중합체의 침전중합
ES90910019T ES2070325T3 (es) 1989-06-26 1990-06-14 Polimerizacion por precipitacion de terpolimeros de una lactama vinilica.
AU58498/90A AU630714B2 (en) 1989-06-26 1990-06-14 Precipitation polymerization of vinyl lactam terpolymers
CA002019556A CA2019556C (en) 1989-06-26 1990-06-21 Precipitation polymerization of terpolymers of a vinyl lactam a polymerizable carboxylic acid and a hydrophobic monomer in an aliphatic hydrocarbon solvent

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Application Number Priority Date Filing Date Title
US07/373,012 US5015708A (en) 1989-06-26 1989-06-26 Precipitation polymerization of terpolymers of a vinyl lactam, a polymerizable carboxylic acid and a hydrophobic monomer in an aliphatic hydrocarbon solvent

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US (1) US5015708A (de)
EP (1) EP0479856B1 (de)
JP (1) JP2991491B2 (de)
KR (1) KR0149171B1 (de)
AT (1) ATE118512T1 (de)
AU (1) AU630714B2 (de)
CA (1) CA2019556C (de)
DE (1) DE69017025T2 (de)
DK (1) DK0479856T3 (de)
ES (1) ES2070325T3 (de)
WO (1) WO1991000302A1 (de)

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WO1992007011A1 (en) * 1990-10-18 1992-04-30 Isp Investments Inc. Swellable, crosslinked polyvinylpyrrolidone and cosmetic compositions therewith
US5130388A (en) * 1991-05-06 1992-07-14 Isp Investments Inc. Precipitation polymerization process
WO1992017509A1 (en) * 1991-04-01 1992-10-15 Isp Investments Inc. Precipitation polymerization process
US5191043A (en) * 1992-03-16 1993-03-02 Isp Investments Inc. Precipitation polmerization of copolymers of a vinyl lactam and a polymerizable carboxylic acid having a molecular weight of less than 20,000 in a cosolvent mixture of an aliphatic hydrocarbon solvent and isopropanol
FR2704771A1 (fr) * 1993-05-07 1994-11-10 Oreal Utilisation d'un terpolymère dérivé de vinyl lactame comme agent de moussage dans des compositions formant une mousse aérosol et composition de mise en Óoeuvre.
US5376447A (en) * 1993-05-25 1994-12-27 Rhone-Poulenc Specialty Chemicals Co. Wallcovering material containing prepaste adhesives
US5387641A (en) * 1993-05-25 1995-02-07 Yeung; Dominic W. K. Aqueous polymer emulsions useful as wallcovering prepaste adhesives
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WO2000030595A1 (en) * 1998-11-23 2000-06-02 Isp Investments Inc. Polymer personal care compositions
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US20050101740A1 (en) * 2003-09-01 2005-05-12 Nathalie Mougin Block ethylenic copolymers comprising a vinyllactam block, cosmetic compositions containing them and cosmetic use of these copolymers
US20050238594A1 (en) * 2003-09-15 2005-10-27 Nathalie Mougin Block ethylenic copolymers comprising a vinyllactam block, cosmetic or pharmaceutical compositions comprising them and cosmetic use of these copolymers
US20060088487A1 (en) * 2003-09-15 2006-04-27 Nathalie Mougin Block ethylenic copolymers comprising a vinyllactam block, cosmetic or pharmaceutical compositions containing them and cosmetic use of these copolymers
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US20060122321A1 (en) * 2004-12-07 2006-06-08 Basf Aktiengesellschaft Method of producing aqueous secondary dispersions of water-insoluble polymers
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US20080199416A1 (en) * 2005-07-22 2008-08-21 Basf Aktiengesellschaft Use of Anionically and Cationically Ampholytic Copolymers
US20080227871A1 (en) * 2005-07-26 2008-09-18 Basf Aktiengesellschaft Ampholytic Copolymer, Production Thereof, and Use of the Same
US20110003956A1 (en) * 2008-02-01 2011-01-06 Basf Se Linear precipitated polymer
US20110004032A1 (en) * 2008-02-28 2011-01-06 Basf Se Method for isomerizing olefinically unsaturated alcohols
US20110218296A1 (en) * 2010-03-02 2011-09-08 Basf Se Anionic associative rheology modifiers
US20110218295A1 (en) * 2010-03-02 2011-09-08 Basf Se Anionic associative rheology modifiers
WO2011107440A1 (en) 2010-03-02 2011-09-09 Basf Se Anionic associative rheology modifiers
WO2011107463A1 (en) 2010-03-02 2011-09-09 Basf Se Anionic associative rheology modifiers
WO2012022668A1 (en) 2010-08-16 2012-02-23 Basf Se Anionic associative rheology modifiers
WO2014160604A1 (en) * 2013-03-26 2014-10-02 Isp Investments Inc. Coating compositions for forming toner coatings
WO2022008359A1 (en) * 2020-07-09 2022-01-13 Basf Se Novel copolymers and their use in pharmaceutical dosage forms

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DE4223066A1 (de) * 1992-07-14 1994-01-20 Basf Ag Haarbehandlungsmittel, die als Filmbildner Copolymerisate enthalten
FR2738010B1 (fr) * 1995-08-24 1997-10-31 Cray Valley Sa Polymeres (meth)acryliques, leur procede de fabrication et leur utilisation comme dispersant de pigment
CA2277484A1 (en) * 1997-01-10 1998-07-16 Robert Polywka Detergent compositions and copolymers for inhibiting dye transfer
US5919484A (en) * 1998-01-15 1999-07-06 Isp Investments Inc. Controlled release, drug-delivery tableted composition including a polymer of a vinyl amide, (meth)acrylic acid, a long chain alkyl (meth)acrylate and a lower alkyl (meth)acrylate
GB0229147D0 (en) 2002-12-13 2003-01-15 Unilever Plc Polymers and laundry detergent compositions containing them
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CN102428111A (zh) * 2009-05-15 2012-04-25 巴斯夫欧洲公司 沉淀聚合物
US8822615B1 (en) * 2013-02-08 2014-09-02 Rohm And Haas Electronic Materials Llc Block copolymer composition and methods relating thereto
US8822616B1 (en) * 2013-02-08 2014-09-02 Rohm And Haas Electronic Materials Llc Block copolymer formulation and methods relating thereto
WO2015059084A1 (de) 2013-10-21 2015-04-30 Basf Se Fällungspolymerisation in gegenwart eines tertiären amins und eines anhydrids
ES2956240T3 (es) 2020-09-29 2023-12-15 Procter & Gamble Composición limpiadora para lavavajillas

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FR2704771A1 (fr) * 1993-05-07 1994-11-10 Oreal Utilisation d'un terpolymère dérivé de vinyl lactame comme agent de moussage dans des compositions formant une mousse aérosol et composition de mise en Óoeuvre.
WO1994026238A1 (fr) * 1993-05-07 1994-11-24 L'oreal Utilisation d'un terpolymere derive de vinyl lactame comme agent de moussage dans des compositions formant une mousse aerosol et composition de mise en ×uvre
US5900229A (en) * 1993-05-07 1999-05-04 L'oreal Use of a vinyl lactam-derived terpolymer as a foaming agent in compositions forming an aerosol foam
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US20060088487A1 (en) * 2003-09-15 2006-04-27 Nathalie Mougin Block ethylenic copolymers comprising a vinyllactam block, cosmetic or pharmaceutical compositions containing them and cosmetic use of these copolymers
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US20080199416A1 (en) * 2005-07-22 2008-08-21 Basf Aktiengesellschaft Use of Anionically and Cationically Ampholytic Copolymers
US20080227871A1 (en) * 2005-07-26 2008-09-18 Basf Aktiengesellschaft Ampholytic Copolymer, Production Thereof, and Use of the Same
US20070104670A1 (en) * 2005-10-28 2007-05-10 Christine Annotel Cosmetic composition comprising at least one specific fixative polymer and at least one sulphonated polymer
WO2008069568A1 (en) * 2006-12-05 2008-06-12 Lg Chem, Ltd. Method for preparing polymer by precipitation polymerization
US20100004412A1 (en) * 2006-12-05 2010-01-07 Seung-Young Park Method for preparing polymer by precipitation polymerization
US8236909B2 (en) 2006-12-05 2012-08-07 Lg Chem, Ltd. Method for preparing polymer by precipitation polymerization
EP2520596A1 (de) 2008-02-01 2012-11-07 Basf Se Lineares Fällungspolymerisat
US20110003956A1 (en) * 2008-02-01 2011-01-06 Basf Se Linear precipitated polymer
US20110004032A1 (en) * 2008-02-28 2011-01-06 Basf Se Method for isomerizing olefinically unsaturated alcohols
US8563785B2 (en) 2008-02-28 2013-10-22 Basf Se Method for isomerizing olefinically unsaturated alcohols
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DE69017025D1 (de) 1995-03-23
WO1991000302A1 (en) 1991-01-10
DK0479856T3 (da) 1995-06-26
ATE118512T1 (de) 1995-03-15
EP0479856B1 (de) 1995-02-15
JP2991491B2 (ja) 1999-12-20
DE69017025T2 (de) 1995-08-10
AU630714B2 (en) 1992-11-05
EP0479856A1 (de) 1992-04-15
CA2019556C (en) 2000-09-26
AU5849890A (en) 1991-01-17
KR0149171B1 (ko) 1998-10-15
KR920702697A (ko) 1992-10-06
EP0479856A4 (en) 1992-12-30
ES2070325T3 (es) 1995-06-01
CA2019556A1 (en) 1990-12-26

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